EP0459720A1 - Metallisierter Mehrschichtfilm - Google Patents

Metallisierter Mehrschichtfilm Download PDF

Info

Publication number
EP0459720A1
EP0459720A1 EP91304728A EP91304728A EP0459720A1 EP 0459720 A1 EP0459720 A1 EP 0459720A1 EP 91304728 A EP91304728 A EP 91304728A EP 91304728 A EP91304728 A EP 91304728A EP 0459720 A1 EP0459720 A1 EP 0459720A1
Authority
EP
European Patent Office
Prior art keywords
layer
substrate
multilayer film
substrate layer
parts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP91304728A
Other languages
English (en)
French (fr)
Other versions
EP0459720B1 (de
Inventor
Kohji c/o Yamagata 3M Limited Suzuki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Co
Original Assignee
Minnesota Mining and Manufacturing Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Publication of EP0459720A1 publication Critical patent/EP0459720A1/de
Application granted granted Critical
Publication of EP0459720B1 publication Critical patent/EP0459720B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
    • B44C1/10—Applying flat materials, e.g. leaflets, pieces of fabrics
    • B44C1/14—Metallic leaves or foils, e.g. gold leaf
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • B32B2255/205—Metallic coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2451/00—Decorative or ornamental articles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/034—Organic insulating material consisting of one material containing halogen
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/036—Multilayers with layers of different types
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/14—Layer or component removable to expose adhesive
    • Y10T428/1424—Halogen containing compound
    • Y10T428/1429—Fluorine
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/14—Layer or component removable to expose adhesive
    • Y10T428/1438—Metal containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/14—Layer or component removable to expose adhesive
    • Y10T428/1462—Polymer derived from material having at least one acrylic or alkacrylic group or the nitrile or amide derivative thereof [e.g., acrylamide, acrylate ester, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24851—Intermediate layer is discontinuous or differential
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24917—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including metal layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2813—Heat or solvent activated or sealable
    • Y10T428/2817—Heat sealable
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2839—Web or sheet containing structurally defined element or component and having an adhesive outermost layer with release or antistick coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31692—Next to addition polymer from unsaturated monomers
    • Y10T428/31699—Ester, halide or nitrile of addition polymer

Definitions

  • This invention relates to metallized multilayer films and, more particularly, to metallized films having a substrate which includes poly(vinylidine fluoride) and poly(methyl methacrylate).
  • Metallized films that is, films comprising a polymeric substrate on which has been deposited a layer of metal, are often employed in, for example, the automotive, furniture, stationery, interior building material, and advertising industries so as to provide an aesthetic or decorative enhancement to manufactured articles.
  • Such films in order to be commercially useful as decorative and aesthetic enhancements, should possess several characteristics.
  • the substrate layer should be highly transparent so as not to detract from the reflective quality of the metal layer and the overall appearance of the article.
  • the films should also exhibit good heat stability, especially when employed in the construction of outdoor signs, motor vehicles and other articles where high temperatures may be encountered. For example, the interior of a motor vehicle on a warm, sunny day in certain climates may experience temperatures in excess of 90°C.
  • metallized multilayer films may be embellished with printed messages, decorative patterns, or complementary decorative transparent, colored layers.
  • Metallized films in order to be commercially useful, should readily accept printing and should be susceptible to the adhesion of further decorative layers thereto. Such films should also possess excellent adhesion between the metal and substrate layers.
  • the films should be capable of being applied in an economical manner and retain a quality appearance without developing bubbles, wrinkles, swells or the like. Once applied, the films should remain durable and exhibit good resistance to a wide variety of weathering and environmental conditions.
  • metallized films which are presently known exhibit some, but not all, of these desirable features.
  • the presently known films may not be broadly employed in a diverse myriad of circumstances.
  • metallized polyester films as described in the plastic Handbook published by Asakura Shoten
  • Various metallized polyester films are commercially available and have been for many years.
  • Metallized films comprising a metal layer deposited on a single layer fluoropolymer substrate have fair heat stability and durability, as well as good adhesion between the metal layer and the fluoropolymer substrate. However, these films are not readily printable. Films of this type are illustrated in Japanese Patent Kokai No. 22973/72, Japanese Patent Kokai No. 71249/85, and Japanese Utility Model Kokai No. 87027/88.
  • a double layer film believed to include a first layer having 80% poly(vinylidine fluoride) and 20% poly(methyl methacrylate) and a second layer having 20% poly(vinylidine fluoride) and 80% poly(methyl methacrylate) is commercially available in Japan from Denki Kagaku Kogyo K.K. as DENKA DX-Film.
  • the film is stated to exhibit excellent weatherability and may be used as a protective cover for metal and plastic boards, as a protective cover for tent clothes, and as a protective or a decorative cover for various substrates.
  • the DENKA DX-Film does not include a metal layer.
  • This invention relates to a metallized multilayer film comprising a first substrate layer, a second substrate layer on the first substrate layer, and a layer of metal on the second substrate layer.
  • the first substrate layer comprises from 0 to about 40 parts by weight poly(vinylidine fluoride) and, correspondingly, from 100 to about 60 parts by weight poly(methyl methacrylate).
  • the second substrate layer comprises from about 70 to 100 parts by weight poly(vinylidine fluoride) and, correspondingly, from about 30 to 0 parts by weight poly(methyl methacrylate).
  • the metal layer may be formed of chromium, nickel, aluminum, stainless steel, tin and alloys thereof and may be in the form of an interrupted pattern on the second substrate layer.
  • the metallized multilayer film may further comprise a layer of an adhesive on the metal layer and a release liner on the adhesive layer.
  • the first substrate layer may further include a printing ink deposited thereon or a layer of a colored resinous material.
  • Metallized multilayer films according to the invention may be applied to the surface of an article so as to provide a decorative and aesthetic enhancement therefor.
  • Metallized multilayer films according to the invention are flexible, durable, heat stable, readily printable, and exhibit good resistance to outdoor weathering.
  • FIG. 1 is an enlarged cross-sectional view of a metallized multilayer film 5 according to the invention.
  • the film 5 comprises a multilayer composite substrate 8 (which, in turn, comprises a first substrate layer 10 and a second substrate layer 20 on the first substrate layer) and a metal layer 30 on the composite substrate 8.
  • the first substrate layer 10 comprises either poly(methyl methacrylate) (PMMA) or a blend of poly(vinylidine fluoride)(PVDF) and PMMA.
  • the PVDF and the PMMA comprising the first substrate layer 10 are preferably combined in a ratio of from 0 to about 40 parts by weight PVDF and, correspondingly, from 100 to about 60 parts by weight PMMA.
  • the second substrate layer 20 comprises either PVDF or a blend of PVDF and PMMA. In the second substrate layer 20, the PVDF and PMMA are preferably combined in a ratio of from about 70 parts to 100 parts by weight PVDF and, correspondingly, from about 30 parts to 0 parts by weight PMMA.
  • poly(vinylidine fluoride) includes both homopolymers of vinylidine fluoride and copolymers comprising vinylidine fluoride and another monomer copolymerizable therewith.
  • suitable comonomers include, for example, vinyl fluoride, tetrafluoroethylene, and chlorotrifluoroethylene.
  • poly(methyl methacrylate), as used herein includes both methyl methacrylate homopolymers and copolymers comprising methyl methacrylate and another monomer copolymerizable therewith.
  • Suitable comonomers include, for example, butyl methacrylate and ethyl methacrylate.
  • the first and second substrate layers 10 and 20, respectively may include various antioxidants, UV stabilizers, and the like so long as they are added in an amount that does not materially adversely affect the ultimate performance of the metallized multilayer film 5.
  • a substrate based on PVDF, PMMA and blends thereof exhibits superior transparency as compared to substrates based exclusively on PVDF, polytetrafluoroethylene or polyvinyl chloride.
  • the transparency of these various substrates was qualitatively compared by vapor coating a layer of alumium thereon with the results shown in Table II below.
  • the PVDF and PMMA in the composite film structure were blended in an arbitrary ratio.
  • the thickness of each sample film was about 50 microns. Table II indicates that film substrates based on PVDF and PMMA exhibit superior transparency over other substrates.
  • the first and second substrate layers 10 and 20, respectively, are combined so as to form the composite substrate layer 8 using conventional techniques such as, for example, coextrusion at a temperature of about 200-300°C or roll pressing at a temperature of about 170-250°C and a pressure of about 5-20 kilograms/square centimeter.
  • the metal layer 30 may be deposited thereon using well known techniques such as, for example, vacuum vapor deposition, sputtering, ion plating or the like.
  • the metal layer 30 may be formed of materials such as chromium, nickel, aluminum, stainless steel, tin and alloys thereof.
  • the metal layer 30 is deposited on the substrate layer having the predominant amount of PVDF, i.e., the second substrate layer 20 herein.
  • the film comprises a composite substrate 8 (which, in turn, comprises first and second substrate layers 10 and 20), and a metal layer 30, all as described more fully hereinabove.
  • the film 5 further comprises an adhesive layer 40 and a release liner 50.
  • Adhesive layer 40 may comprise any of a wide variety of conventionally known adhesive materials including, for example, acrylic, rubber, silicone resin and heat curable epoxy adhesives.
  • the adhesive layer 40 is applied to the surface of the metal layer 30 opposite the surface which engages the second substrate layer 20.
  • Release liner 50 is applied to the exposed surface of the adhesive layer 40 and protects the adhesive layer until the film 5 is ready for use.
  • release liner 50 is removed thereby exposing adhesive layer 40.
  • the film 5 is then placed on the surface (not shown separately in the drawings) to which the film is to be applied and pressure is applied to the film for a time sufficient to strongly adhere the same to the surface.
  • a third embodiment of a metallized multilayer film 5 according to the invention is illustrated in the enlarged cross-sectional view of FIG. 3.
  • the metallized multilayer film 5 is similar to that shown in FIG. 1 and comprises a composite substrate layer 8 (which, in turn, comprises first and second substrate layers 10 and 20 respectively), and a layer of metal 30, which metal layer has been applied to the second substrate layer in an interrupted arrangement so as to provide a decorative pattern.
  • the film 5 thereof may also include an adhesive layer and a release liner as described in conjunction with FIG. 2.
  • the first substrate layer 10 may further include a printing ink or a layer of a colored resinous material deposited thereon.
  • Suitable printing inks include, for example, acrylic and polyvinyl chloride/acetate copolymer inks.
  • Suitable resinous materials include, as examples, laminates which incorporate polyvinyl chloride or an acrylate resin.
  • a series of metallized films comprising a layer of aluminum deposited on different substrates was prepared.
  • the substrates comprised a single PVDF/PMMA layer, the examples varying in the relative proportions of PVDF and PMMA.
  • the samples were then evaluated for their heat stability and their ability to adhere a printing ink.
  • Ability to adhere a printing ink was determined by applying an acrylic ink (SCOTCHCAL 3903 brand screen ink, commercially available from the Minnesota Mining and Manufacturing Co., St. Paul, Minnesota) and a polyvinyl chloride/acetate copolymer ink (SCOTCHCAL 3920 brand screen ink, commercially available from the Minnesota Mining and Manufacturing Co., St. Paul, Minnesota) and evaluating for peel adhesion.
  • the inks were screen printed onto the substrate materials through a 270 mesh screen, dried at 65°C for two hours, and then allowed to cool at room temperature for about one hour. The ink layer was then cut through (without harming the underlying substrate) to form a grid or lattice pattern.
  • a strip of SCOTCH 610 brand cellophane tape (commercially available from the Minnesota Mining and Manufacturing Co., St. Paul, Minnesota) was applied over the ink layer and firmly pressed thereto. The tape was then peeled from the film in a single continuous motion. If the ink remained on the substrate in good condition, the substrate was considered as having good adhesion to the printing ink. The results are shown below in Table III.
  • Table III shows that substrates comprising PVDF and PMMA in the range of about 70 parts to 100 parts by weight PVDF and, correspondingly, from about 30 parts to 0 parts by weight PMMA exhibit good heat stability, even at temperatures of about 120°C.
  • the substrate layer in which the PVDF predominates contributes to the heat stability of the overall article.
  • the substrate layer in which the PMMA predominates demonstrates good adhesion to printing inks.
  • the outermost substrate layer i.e. the first substrate layer 10 herein
  • the innermost substrate layer i.e. the second substrate layer 20 on which the metal layer may be deposited

Landscapes

  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP91304728A 1990-05-31 1991-05-24 Metallisierter Mehrschichtfilm Expired - Lifetime EP0459720B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2143278A JPH0435938A (ja) 1990-05-31 1990-05-31 金属調光沢を有する積層フィルム
JP143278/90 1990-05-31

Publications (2)

Publication Number Publication Date
EP0459720A1 true EP0459720A1 (de) 1991-12-04
EP0459720B1 EP0459720B1 (de) 1996-03-06

Family

ID=15335023

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91304728A Expired - Lifetime EP0459720B1 (de) 1990-05-31 1991-05-24 Metallisierter Mehrschichtfilm

Country Status (5)

Country Link
US (1) US5164245A (de)
EP (1) EP0459720B1 (de)
JP (1) JPH0435938A (de)
CA (1) CA2042995A1 (de)
DE (1) DE69117584T2 (de)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994003337A3 (en) * 1992-07-31 1994-05-26 Paint film and methods for its manufacture
WO1994012583A1 (en) * 1992-12-01 1994-06-09 Minnesota Mining And Manufacturing Company Heat transferable fluorinated resin film
WO1994019769A3 (en) * 1993-02-16 1995-04-27 Minnesota Mining & Mfg System and method for manufacturing improved data display retroreflective sheeting
WO1996010491A1 (en) * 1994-09-30 1996-04-11 Kimberly-Clark Corporation Composite for transfer of durable graphics
US5508105A (en) * 1993-02-16 1996-04-16 Minnesota Mining And Manufacturing Company Thermal print receptive and frangible retrorefelective polymeric sheetings
WO1996035969A1 (en) * 1995-05-12 1996-11-14 Minnesota Mining And Manufacturing Company Retroreflective sheet and article having retroreflectiveness
US5670005A (en) * 1993-02-16 1997-09-23 Minnesota Mining And Manufacturing Company Method for manufacturing improved data display retroreflective sheeting
WO1999038901A1 (en) * 1998-01-30 1999-08-05 Minnesota Mining And Manufacturing Company Decorative sheet
US5985079A (en) * 1996-03-28 1999-11-16 Rexam Industries Corp. Flexible composite surfacing film and method for producing same
WO2000023287A1 (en) * 1998-10-16 2000-04-27 Minnesota Mining And Manufacturing Company Decorative film and method for the production of the same
WO2000034405A1 (en) * 1998-12-10 2000-06-15 Minnesota Mining And Manufacturing Company Adhesive compositions and adhesive sheets
US6296732B1 (en) * 1995-06-07 2001-10-02 Avery Dennison Corporation Extrusion process for protective coatings for outdoor siding panels and the like
US6383613B1 (en) 1998-10-16 2002-05-07 3M Innovative Properties Company Decorative film and method for the production of the same
US6458464B1 (en) 1998-12-28 2002-10-01 3M Innovative Properties Company Decorative sheet
US6627688B1 (en) 1998-12-10 2003-09-30 3M Innovative Properties Company Adhesive compositions and adhesive sheets
EP1462243A1 (de) * 2003-03-26 2004-09-29 Hueck Folien GmbH & Co. KG Verpackungsverbundfolie
US10345495B2 (en) 2014-12-30 2019-07-09 3M Innovative Properties Company Stain resistant retroreflective articles

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6071621A (en) * 1993-06-11 2000-06-06 3M Innovative Properties Company Metallized film and decorative articles made therewith
ZA964731B (en) 1995-06-07 1997-01-07 Avery Dennison Corp A Legal Bo Extrusion coating process for making protective and decorative films
US6254712B1 (en) 1998-12-08 2001-07-03 Avery Dennison Corporation Extrusion coating process for making high transparency protective and decorative films
US20040209057A1 (en) * 1995-06-07 2004-10-21 Enlow Howard H. Extruded polymeric high transparency films
US5855353A (en) * 1996-05-31 1999-01-05 Owens Corning Fiberglas Technology, Inc. Vibration damping system
US5848769A (en) * 1996-08-26 1998-12-15 Minnesota Mining & Manufacturing Company Drag reduction article
US5865931A (en) * 1997-02-10 1999-02-02 Aluminum Company Of America Reflective vehicle trim
US6413630B1 (en) 1997-05-15 2002-07-02 3M Innovative Properties Company Decorative film
US6174578B1 (en) * 1997-10-24 2001-01-16 Rexam Industries Corp. Radiation deactivatable adhesive tape
US6287672B1 (en) * 1999-03-12 2001-09-11 Rexam, Inc. Bright metallized film laminate
US6346318B1 (en) * 1999-10-18 2002-02-12 M & R Plastics Inc. Metallized colored transparent laminating film
US6942911B2 (en) * 2000-04-27 2005-09-13 3M Innovative Properties Company Display member having metallic luster
US7609512B2 (en) 2001-11-19 2009-10-27 Otter Products, Llc Protective enclosure for electronic device
US20030180564A1 (en) * 2001-12-14 2003-09-25 Torsten Marquardt Surface film for laminating on to a substrate
FR2850975B1 (fr) * 2003-02-07 2006-07-07 Atofina Objet fabrique avec un film multicouche metallise ou une structure multicouche comprenant une couche de liant a base de pe et llpde
DE10307386A1 (de) * 2003-02-21 2004-09-09 Dieter Wildfang Gmbh Verfahren zum außenseitigen Beschichten eines sanitären Auslaufteiles sowie sanitäres Auslaufteil
US20040219366A1 (en) * 2003-05-02 2004-11-04 Johnson John R. Bright formable metalized film laminate
CN100474642C (zh) * 2005-10-27 2009-04-01 晶能光电（江西）有限公司 含有金属铬基板的铟镓铝氮半导体发光元件及其制造方法
JP5269364B2 (ja) * 2007-08-03 2013-08-21 株式会社日本触媒 フィルム及びその製造方法
WO2010019251A2 (en) * 2008-08-13 2010-02-18 Vacumet Corp. Metallized barrier material
US8668166B2 (en) * 2009-01-29 2014-03-11 The Boeing Company Shape memory riblets
EP3373712B1 (de) * 2017-03-09 2023-03-29 MGI Digital Technology Verfahren zur aufbringung von leiterbahnen

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3915779A (en) * 1973-07-10 1975-10-28 Kureha Chemical Ind Co Ltd Method for effecting vacuum evaporation
US4068034A (en) * 1974-02-12 1978-01-10 Kureha Kagaku Kogyo Kabushiki Kaisha Heat-insulation laminate of polyvinylidene fluoride, metal and plastic
EP0133821A2 (de) * 1983-08-10 1985-03-06 Minnesota Mining And Manufacturing Company Schichtstoffe zum Aufbringen von graphischen Darstellungen die Bereiche aufweisen, die sowohl metallartig als auch gemustert aussehen
EP0154339A2 (de) * 1984-03-06 1985-09-11 Sumitomo Chemical Company, Limited Optische Faser
US4810320A (en) * 1986-03-18 1989-03-07 Hiromichi Inagaki Method of selectively forming an aluminum evaporation face

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6071249A (ja) * 1983-09-28 1985-04-23 日立化成工業株式会社 複合材料の製造法
JPS6387027A (ja) * 1986-09-30 1988-04-18 Matsushita Electric Ind Co Ltd ハウリング抑圧装置
US5030394A (en) * 1988-11-08 1991-07-09 Labofina, S.A. PVdF-based powder coatings

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3915779A (en) * 1973-07-10 1975-10-28 Kureha Chemical Ind Co Ltd Method for effecting vacuum evaporation
US4068034A (en) * 1974-02-12 1978-01-10 Kureha Kagaku Kogyo Kabushiki Kaisha Heat-insulation laminate of polyvinylidene fluoride, metal and plastic
EP0133821A2 (de) * 1983-08-10 1985-03-06 Minnesota Mining And Manufacturing Company Schichtstoffe zum Aufbringen von graphischen Darstellungen die Bereiche aufweisen, die sowohl metallartig als auch gemustert aussehen
EP0154339A2 (de) * 1984-03-06 1985-09-11 Sumitomo Chemical Company, Limited Optische Faser
US4810320A (en) * 1986-03-18 1989-03-07 Hiromichi Inagaki Method of selectively forming an aluminum evaporation face

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994003337A3 (en) * 1992-07-31 1994-05-26 Paint film and methods for its manufacture
WO1994012583A1 (en) * 1992-12-01 1994-06-09 Minnesota Mining And Manufacturing Company Heat transferable fluorinated resin film
US5670005A (en) * 1993-02-16 1997-09-23 Minnesota Mining And Manufacturing Company Method for manufacturing improved data display retroreflective sheeting
WO1994019769A3 (en) * 1993-02-16 1995-04-27 Minnesota Mining & Mfg System and method for manufacturing improved data display retroreflective sheeting
TR28165A (tr) * 1993-02-16 1996-02-08 Minnesota Mining & Mfg Islah edilmis veri görüntülü geri yansitmali tabakanin imalatina yönelik sistem ve metod.
US5508105A (en) * 1993-02-16 1996-04-16 Minnesota Mining And Manufacturing Company Thermal print receptive and frangible retrorefelective polymeric sheetings
WO1996010491A1 (en) * 1994-09-30 1996-04-11 Kimberly-Clark Corporation Composite for transfer of durable graphics
WO1996035969A1 (en) * 1995-05-12 1996-11-14 Minnesota Mining And Manufacturing Company Retroreflective sheet and article having retroreflectiveness
US5714223A (en) * 1995-05-12 1998-02-03 Minnesota Mining And Manufacturing Company Retroreflective sheet and article having retroreflectiveness
AU697421B2 (en) * 1995-05-12 1998-10-08 Minnesota Mining And Manufacturing Company Retroreflective sheet and article having retroreflectiveness
CN1095082C (zh) * 1995-05-12 2002-11-27 美国3M公司 具有逆向反射性的制品
US6296732B1 (en) * 1995-06-07 2001-10-02 Avery Dennison Corporation Extrusion process for protective coatings for outdoor siding panels and the like
US5985079A (en) * 1996-03-28 1999-11-16 Rexam Industries Corp. Flexible composite surfacing film and method for producing same
WO1999038901A1 (en) * 1998-01-30 1999-08-05 Minnesota Mining And Manufacturing Company Decorative sheet
US6383613B1 (en) 1998-10-16 2002-05-07 3M Innovative Properties Company Decorative film and method for the production of the same
WO2000023287A1 (en) * 1998-10-16 2000-04-27 Minnesota Mining And Manufacturing Company Decorative film and method for the production of the same
WO2000034405A1 (en) * 1998-12-10 2000-06-15 Minnesota Mining And Manufacturing Company Adhesive compositions and adhesive sheets
US6627688B1 (en) 1998-12-10 2003-09-30 3M Innovative Properties Company Adhesive compositions and adhesive sheets
US6458464B1 (en) 1998-12-28 2002-10-01 3M Innovative Properties Company Decorative sheet
EP1462243A1 (de) * 2003-03-26 2004-09-29 Hueck Folien GmbH & Co. KG Verpackungsverbundfolie
US10345495B2 (en) 2014-12-30 2019-07-09 3M Innovative Properties Company Stain resistant retroreflective articles

Also Published As

Publication number Publication date
US5164245A (en) 1992-11-17
DE69117584D1 (de) 1996-04-11
EP0459720B1 (de) 1996-03-06
JPH0435938A (ja) 1992-02-06
CA2042995A1 (en) 1991-12-01
DE69117584T2 (de) 1996-10-31

Similar Documents

Publication Publication Date Title
US5164245A (en) Metallized multilayer film
EP1293339A4 (de) Laminierter polyesterfilm
EP0473254A2 (de) Dekorfilm für Gegenstand aus Gummi
US4916008A (en) Plastic molding
GB2097721A (en) Moulding with encapsulated metal film
US5622783A (en) Pressure-sensitive adhesive and a pressure-sensitive comprising construction containing a layer of the adhesive
CA2287908A1 (en) Decorative film
CA2120608A1 (en) Microporous pressure sensitive adhesive coated sheeting
JP2571401B2 (ja) 成形性の優れた金属光沢シート
JP3139439B2 (ja) 化粧シート
JPH06238842A (ja) 新規なる表面硬度改質板とその製法
JP2520273B2 (ja) 耐候性メタリックフイルムの製造方法
CN218710105U (zh) 一种镀铝膜
JPH0518142Y2 (de)
JPH01188334A (ja) メタリック化粧シート
JPH08118556A (ja) 化粧シート
JPH0374909B2 (de)
CN218811490U (zh) 一种氛围灯使用的挡光胶带
JP2555527B2 (ja) 一体成形用Ａｌ積層フイルム
JPH0627407Y2 (ja) モールデイングの光輝テープ
JPH01114434A (ja) 窓貼り用積層材料
JP2857254B2 (ja) 化粧シートの製造方法
JP3993317B2 (ja) 積層フィルム
JPS63182143A (ja) 金属サツシ外装用メタリツク化粧シ−ト
JPH0834090A (ja) 金属化粧板及びその製造方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB IT SE

17P Request for examination filed

Effective date: 19920601

17Q First examination report despatched

Effective date: 19931105

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

ITF It: translation for a ep patent filed
AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB IT SE

REF Corresponds to:

Ref document number: 69117584

Country of ref document: DE

Date of ref document: 19960411

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20080529

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20080630

Year of fee payment: 18

Ref country code: SE

Payment date: 20080529

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20080529

Year of fee payment: 18

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20090524

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20100129

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090602

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20080519

Year of fee payment: 18

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090524

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20091201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090524

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090525